EP0369517B1 - Reaktive Schmelzzusammensetzung - Google Patents

Reaktive Schmelzzusammensetzung Download PDF

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Publication number
EP0369517B1
EP0369517B1 EP89202777A EP89202777A EP0369517B1 EP 0369517 B1 EP0369517 B1 EP 0369517B1 EP 89202777 A EP89202777 A EP 89202777A EP 89202777 A EP89202777 A EP 89202777A EP 0369517 B1 EP0369517 B1 EP 0369517B1
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EP
European Patent Office
Prior art keywords
diol
polycarbonate
prepared
component
melt composition
Prior art date
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EP89202777A
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English (en)
French (fr)
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EP0369517A1 (de
Inventor
Alberto Greco
Sergio Giordano
Enrico Pozzi
Patrizia Blasioli
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Enichem Sintesi SpA
Boston SpA
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Enichem Sintesi SpA
Boston SpA
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Priority to AT89202777T priority Critical patent/ATE92508T1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/20—Compositions for hot melt adhesives

Definitions

  • This invention relates to a reactive hot melt composition and its preparation process.
  • Reactive hot melts are known products of the art and are used mainly in the vehicle industry, in bookbinding, in the textile industry, in the wood industry and in cellular manufacture.
  • One known class of reactive hot melts is that based on prepolymers carrying free NCO groups at their chain ends, and is prepared by reacting a diisocyanate with a polyester, especially an aliphatic polyadipate diol, having hydroxyl termination.
  • a polyester especially an aliphatic polyadipate diol, having hydroxyl termination.
  • H.F. Huber and H. Muller Adhesive Age, Nov. 1987, page 32.
  • the main drawback in the use of polyesters is their hydrolytic instability, with the result that crosslinked hot melts suffer in the medium or long term from mechanical weakening and loss of adhesion.
  • EP-A-89,180 discloses a crystalline end-blocked polyurethane prepolymer obtained by reacting an organic polyisocyanate, a long chain crystalline polyol, a polyhydroxy cross-linking agent and a short chain diol extender.
  • the object of the present invention is to overcome these drawbacks of the state of the art by new polycarbonate-based hot melt compositions possessing good general characteristics and having high resistance to degradation.
  • a reactive low-melting solid hot-melt composition which is cross-linkable by environmental humidity or heat to form products highly resistant to degradation and has a melting point temperature of from 30°C and 70°C, a viscosity of from 10 Pa.s to 50 Pa.s at 105°C, and a glass-transition temperature (T g ) of from -60°C to 50°C, comprised of the product of the reaction of:
  • the diol mixture (B) contains between 30 and 50 parts by weight of component (B1), between 30 and 70 parts by weight of component (B2) and between 0 and 40 parts by weight of component (B3) per 100 parts by weight of the sum of (B1), (B2) and (B3), and the ratio of NCO groups of component (A) to OH groups of component (B) is between 1.5 and 2.2.
  • the aliphatic and aromatic diisocyanates (A) usable for the purpose of the invention can be chosen from diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, tetramethyl xylylene diisocyanate, phenylene diisocyanate and tolylene diisocyanate. Either pure diisocyanates can be used or technical diisocyanates containing a fraction of polyisocyanates.
  • the crystalline polycarbonate diol (B1) is a solid product with a melting point normally in the range of 50-70°C, a high crystallization rate, a ⁇ H of fusion normally in the range of 80-115 J/g and a hydroxyl functionality equal to or greater than 95% of theoretical. Its number-average molecular weight (Mn) is preferably between 2,000 and 4,000.
  • This crystalline polycarbonate diol is prepared from an organic carbonate and an HO-(CH2) x -OH aliphatic diol, where x is a whole number equal to or greater than 8.
  • the organic carbonate can be a dialkyl carbonate, a dialkylene carbonate, a cycloalkylene carbonate or a diaryl carbonate.
  • Diallyl carbonate is preferably used.
  • the aliphatic diol is preferably chosen from 1,10-decanediol and 1,12-dodecanediol.
  • the transesterification is normally conducted with a diol/organic carbonate ratio of between 1.03 and 1.3 at a temperature of between about 80°C and about 200°C for a time of between about 4 and about 10 hours, the alcohol, glycol and phenol which form as by-products being removed. To facilitate this removal it is convenient to operate at reduced pressure, for example 6,67 KPa - 26,66 KPa (50-200 torr), at least during the final part of the reaction.
  • the organic carbonate is a dialkyl carbonate or a dialkylene carbonate
  • a transesterification catalyst preferably of alkaline type, for example an alkaline alcoholate such as sodium methylate.
  • the elastomeric polycarbonate diol or elastomeric polycarbonate copolyester diol (B2) is either a liquid at ambient temperature or a low-melting solid (melting point up to about 50°C), with hydroxyl functionality equal to or greater than 95% of theoretical. Its number-average molecular weight (Mn) varies preferably from 2,000 to 4,000 and its glass transition temperature (Tg) varies preferably from -50°C to -60°C.
  • the elastomeric polycarbonate diol is prepared from an organic carbonate, preferably diallyl carbonate, and an HO-(CH2) y -OH aliphatic diol, where y is a whole number less than 8, operating under the aforedescribed transesterification conditions.
  • the aliphatic diol is preferably 1,5-pentanediol or 1,6 hexanediol or mixtures of the two.
  • the elastomeric polycarbonate copolyester diol (B2) can be prepared from an organic carbonate, an HO-(CH2) y -OH aliphatic diol, where y has the aforesaid meaning (and preferably 1,5-pentanediol, 1,6-hexanediol or mixtures of the two), and a lactone, preferably caprolactone, operating under the aforedescribed transesterification conditions.
  • a caprolactone quantity of between 15 and 30% w/w of the sum of the moles of diol and caprolactone.
  • the elastomeric polycarbonate copolyester diol can also be prepared under the aforedescribed transesterification conditions, from the organic carbonate, the HO-(CH2) y -OH diol, where y has the aforesaid meaning (and preferably 1,5-pentanediol, 1,6-hexanediol or mixtures of the two), and an aliphatic polyester diol oligomer.
  • said oligomer can be prepared by condensing an aliphatic dicarboxylic acid, normally chosen from succinic, adipic, sebacic and dodecanoic acids, an HO-(CH2) y -OH aliphatic diol, where y has the aforesaid meaning (and preferably 1,5-pentanediol, 1,6-hexanediol or mixtures of the two), and neopentyl glycol, in a molar ratio of between 4/1 and 1/1, operating at a temperature of between 100°C and 250°C, with continual removal of the water which is evolved as reaction by-product. The reaction is continued until an oligomer is obtained having a number-average molecular weight (Mn) from about 350 to about 750.
  • Mn number-average molecular weight
  • the vitreous polycarbonate diol or vitreous polycarbonate copolyester diol (B3) is a normally solid product, with a number-average molecular weight (Mn) preferably in the range of 700 to 3,000.
  • the vitreous polycarbonate diol is prepared under the aforedescribed transesterification conditions from an organic carbonate and a cycloaliphatic diol preferably chosen from cyclohexanedimethanol and tricyclohexanedimethanol. A mixture of cycloaliphatic and aliphatic diols can also be used.
  • the vitreous polycarbonate copolyester diol (B3) is prepared under the aforedescribed transesterification conditions from an organic carbonate, a cycloaliphatic diol (preferably cyclohexanedimethanol or tricyclodecanedimethanol) or a mixture of cycloaliphatic and aliphatic diols, and an aromatic polyester dial oligomer.
  • This latter is produced by condensing an aromatic acid, such as phthalic, isophthalic or terephthalic acid and a cycloaliphatic diol (preferably cyclohexanedimethanol or tricyclodecane dimethanol), in a molar ratio of between 2/1 and 4/3, operating under the aforedescribed conditions, until an oligomer is obtained having a number-average molecular weight (Mn) from about 500 to about 1000.
  • aromatic acid such as phthalic, isophthalic or terephthalic acid
  • a cycloaliphatic diol preferably cyclohexanedimethanol or tricyclodecane dimethanol
  • the reactive hot melt composition according to the present invention is prepared by reacting the diisocyanate (A) with the diol mixture (B) within the aforedefined ratio range.
  • the reaction is conducted in bulk or with the possible addition of a small quantity of diluent to reduce the viscosity of the reaction mixture, operating at a temperature below 110°C, and preferably within the range of 60-100°C, for a time generally between 0.5 and 6 hours.
  • Small quantities of an organometallic tin, lead, mercury or titanium catalyst can be present. If used, the catalyst is present in a quantity of less than 0.2% by weight and generally between 0.05 and 0.1% by weight with respect to component (B). However, in the preferred embodiment, the process is carried out without catalyst.
  • the reactive hot melt compositions according to the present invention are obtained in the form of a low-melting solid (melting point between about 30°C and about 70°C), having a viscosity of between about 10 and about 50 Pa.s measured at 105°C and a glass transition temperature (Tg) of between about -60 and about 50°C.
  • Tg glass transition temperature
  • the reactive hot melt compositions according to the present invention can also contain cross-linking catalysts (such as tertiary amines and organometallic tin compounds), adhesion promoters (such as functionalized trialkoxysilanes), inorganic fillers (such as carbon, calcium carbonate and talc), antioxidants and stabilizers (such as sterically hindered amines, sterically hindered phenols, hydroxybenzotriazoles and hydroxybenzophenones), flame retardants and resinous tackiness agents (such as butadiene acrylonitrile resins).
  • cross-linking catalysts such as tertiary amines and organometallic tin compounds
  • adhesion promoters such as functionalized trialkoxysilanes
  • inorganic fillers such as carbon, calcium carbonate and talc
  • antioxidants and stabilizers such as sterically hindered amines, sterically hindered phenols, hydroxybenzotriazoles and hydroxybenz
  • Transesterification of diallyl carbonate with 1,10-decanediol is conducted under the conditions reported in the description using a molar 1,10-decanediol/diallyl carbonate ratio of 1.1 and 1.09 to prepare the crystalline polycarbonate diols of Examples 1 and 2 respectively.
  • the crystalline polycarbonate diols of Examples 3 and 4 are likewise prepared using 1,12-dodecanediol, with a molar 1,12-dodecanediol/diallyl carbonate ratio of 1.11 and 1.05 respectively.
  • An elastomeric polycarbonate diol is prepared (Example 5) by transesterification of 1,6-hexanediol with diallyl carbonate in a molar ratio of 1.075. This product has an unsaturation content of less than 0.01 meq/g and a hydroxyl functionality exceeding 99% of theoretical.
  • Another elastomeric polycarbonate diol (Example 6) is likewise prepared from a mixture of 1,6-hexanediol and 1,5-pentanediol (molar ratio 60/40), operating with a molar diol/diallyl carbonate ratio of 1.08. The product obtained has an unsaturation content of less than 0.01 meq/g.
  • An elastomeric polycarbonate copolyester diol is also prepared (Example 7) by transesterification of 1,6-hexanediol, caprolactone and diallyl carbonate, with a molar 1,6-hexanediol/caprolactone ratio of 67/33 and a molar 1,6-hexanediol/diallyl carbonato ratio of 1.077.
  • an elastomeric polycarbonate copolyester diol is prepared (Example 8) by transesterification using diallyl carbonate (1.91 moles), 1,6-hexanediol (1.5 moles) and a polyester diol oligomer (0.6 moles).
  • the polyester diol oligomer is the product of condensation, conducted as reported in the description, between neopentyl glycol, 1,6-hexanediol and sebacic acid, in a molar ratio of 1:1:1, and has a number-average molecular weight (Mn) of 435 and an acid number of less than 1 mg KOH/g.
  • Mn number-average molecular weight
  • Both the polycarbonate copolyester diols have an unsaturation content of less than 0.01 meq/g.
  • the characteristics of the elastomeric polycarbonate diols and elastomeric polycarbonate copolyester diols are shown in Table 2. TABLE 2 Ex. No. 5 6 7 8 OH No.
  • a vitreous polycarbonate diol is prepared (Example 9) by a transesterification reaction from cyclohexanedimethanol (isomer mixture) and diallyl carbonate in a molar ratio of 1.25. This product has an unsaturation content of less than 0.01 meq/g.
  • a vitreous polycarbonate copolyester diol is likewise prepared (Example 10) from cyclohexanedimethanol (isomer mixture), 1,6-hexanediol and an oligopolyester diol (molar ratio 55:35:10), together with diallyl carbonate with a molar diol/diallyl carbonate ratio of 1.123.
  • the oligopolyester diol is prepared by condensing terephthalic acid (0.63 moles) and dimethanol tricyclodecane (2.2 moles) and has an hydroxyl number of 146.9 mg KOH/g, a glass transition temperature (Tg) of 33.1°C, an acid number of 2 mg KOH/g and a number-average molecular weight (Mn) of 762.
  • a vitreous polycarbonate copolyester diol is prepared (Example 11) from cyclohexanedimethanol (isomer mixture) and the oligopolyester diol described heretofore (in a molar ratio of 89:11) and diallyl carbonate with a diol/diallyl carbonate ratio of 1.13.
  • the polycarbonate copolyester diols of Examples 10 and 11 have an unsaturation content of less than 0.01 meq/g and their characteristics are given in Table 3, together with those of the polycarbonate diol of Example 9. TABLE 3 Ex. No. 9 10 11 OH No.
  • a total of 100 parts of polycarbonates together with 20 ml of xylene and 200 ppm of dibutyltin laurate are fed into a flask fitted with a bladed mechanical stirrer.
  • the polycarbonates are melted (about 65°C) and the diisocyanate is added in the molten state in a single portion under a dry nitrogen atmosphere while stirring.
  • a temperature rise of 12-18°C occurs during the initial minutes of the reaction, after which the temperature of the reaction mass is raised to 95°C over a period of 30 minutes and kept at this value for 60 minutes, after which the xylene is eliminated at 0,27 KPa (2 torr) over about 30 minutes.
  • Example 12 100 parts by weight of the crystalline polycarbonate diol of Example 4 are reacted with diphenylmethane diisocyanate in a NCO/OH ratio of 2.2; in Example 13 (comparison), 100 parts by weight of the crystalline polycarbonate diol of Example 4 are reacted with diphenylmethane diisocyanate in a NCO/OH ratio of 1.5; in Example 14 (comparison), 100 parts by weight of the elastomeric polycarbonate diol of Example 5 are reacted with diphenylmethane diisocyanate in a NCO/OH ratio of 2.2; in Example 15, 50 parts by weight of the crystalline polycarbonate diol of Example 2 and 50 parts by weight of the elastomeric polycarbonate copolyester diol of Example 8 are
  • This product is formed into a cross-linked sheet having the following characteristics: open time 15 seconds, tensile 260 kg/cm2, elongation 780%, yield 70 kg/cm2. After ageing in water at 50°C for 30 days, the following characteristics are found: tensile 250 kg/cm2, elongation 550%, yield 98 kg/cm2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Fats And Perfumes (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Polyesters Or Polycarbonates (AREA)

Claims (14)

  1. Verfahren zur Herstellung einer reaktiven,niedrigschmelzenden, festen Heißschmelzzusammensetzung, die durch umgebende Feuchtigkeit oder Wärme zu gegenüber einem Abbau hochbeständigen Produkten vernetzbar ist und einen Schmelzpunktbereich von 30° C bis 70° C, eine Viskosität bei 105° C von 10 Pa.s bis 50 Pa.s und eine Glasübergangstemperatur (Tg) von -60° C bis 50° C aufweist, umfassend die Stufe des Umsetzens:
    (A) eines aliphatischen oder eines aromatischen Diisocyanats mit
    (B) einem Diolgemisch, bestehend aus:
    (B1) einem kristallinen Polycarbonatdiol mit einem zahlenmittleren Molekulargewicht (Mn) von 1000 bis 10.000, einer Glasübergangstemperatur (Tg) von unter -50° C und einem Mindestkristallisations-ΔH-Wert von 80 J/g, das durch Umesterung eines organischen Carbonats mit wenigstens einem aliphatischen Diol HO-(CH)x-OH hergestellt wird, worin x eine ganze Zahl gleich oder größer als 8 bedeutet;
    (B2) einem elastomeren Polycarbonatdiol oder einem elastomeren Polycarbonat-Copolyesterdiol mit einem zahlenmittleren Molekulargewicht (Mn) von 1.500 bis 6.000 und einer Glasübergangstemperatur (Tg) von -35° C bis -60° C, das durch Umesterung eines organischen Carbonats mit wenigstens einem Diol HO-(CH₂)y-OH hergestellt wird, worin y eine ganze Zahl gleich oder kleiner als 8 bedeutet, wobei das elastomere Polycarbonat-Copolyesterdiol, soferne vorhanden, durch Umesterung eines organischen Carbonats und wenigsten eines aliphatischen Diols HO-(CH₂)y-OH mit entweder einem Lacton oder einem aliphatischen Polyesterdiol-Oligomer hergestellt wird, und
    (B3) einem glasigen Polycarbonatdiol oder einem glasigen Polycarbonat-Copolyesterdiol mit einem zahlenmittleren Molekulargewicht (Mn) von 600 bis 6.000 und einer Glasübergangstemperatur (Tg) von -10° C bis +50° C, welches glasige Polycarbonatdiol durch Umesterung eines organischen Carbonats mit einem cykloaliphatischen Diol oder einem Gemisch von cykloaliphatischen und aliphatischen Diolen hergestellt wird und welches glasige Polycarbonat-Copolyesterdiol, soferne vorhanden, durch Umsetzung eines organischen Carbonats, eines cykloaliphatischen Diols oder eines Gemisches von cykloaliphatischen und aliphatischen Diolen mit einem aromatischen Polyesterdiol-Oligomer mit einem mittleren Molekulargewicht (Mn) von 500 bis 1.000 hergestellt wird, wobei das letztgenannte aromatische Polyesterdiol-Oligomer seinerseits durch Kondensieren einer aromatischen Säure mit einem cykloaliphatischen Diol in einem Molverhältnis von 2:1 bis 4:3 hergestellt wird,
    wobei in 100 Gewichtsteilen der Summe der Diolkomponenten (B1), (B2) und (B3):
    die Diolkomponente (B1) in einer Menge von 30 bis 70 Gew.-Teilen vorliegt;
    die Diolkomponente (B2) in einer Mindestmenge von 20 Gew.-Teilen vorliegt;
    die Diolkomponente (B3) in einer Menge von 0 bis 50 Gew.-Teilen vorliegt;
    und wobei das Verhältnis der in der Diisocyanatkomponente (A) vorliegenden NCO-Gruppen zu den im Diolgemisch (B) vorliegenden OH-Gruppen größer als 1 ist.
  2. Verfahren nach Anspruch 1, wobei in 100 Gew.-Teilen des Diolgemisches (B):
    von 30 bis 50 Gew.-Teile der Diolkomponente (B1) vorliegen;
    von 30 bis 70 Gew.-Teile der Diolkomponente (B2) vorliegen; und
    von 0 bis 40 Gew.-Teile der Diolkomponente (B3) vorliegen;
    wobei das Verhältnis der in der Diisocyanatkomponente (A) vorliegenden NCO-Gruppen zu den im Diolgemisch (B) vorliegenden OH-Gruppen von 1,5 bis 2,2 beträgt.
  3. Verfahren nach Anspruch 1, worin die Diisocyanatkomponente (A) unter
    Diphenylmethandiisocyanat, Isophorondiisocyanat, Hexamethylendiisocyanat, Tetramethylxylylendiisocyanat, Phenylendiisocyanat und Tolylendiisocyanat
    ausgewählt ist.
  4. Verfahren nach Anspruch 1, worin die Diolkomponente (B1) ein zahlenmittleres Molekulargewicht (Mn) von 2.000 bis 4.000 und einen ΔH-Wert der Kristallisation von 80 J/g bis 115 J/g aufweist.
  5. Verfahren nach Anspruch 4, worin die Diolkomponente (B1) durch Umesterung von Diallylcarbonat mit 1,10-Decandiol oder 1,12-Dodecandiol oder mit einem Gemisch beider hergestellt wird.
  6. Verfahren nach Anspruch 1, worin die Diolkomponente (B2) ein zahlenmittleres Molekulargewicht (Mn) von 2.000 bis 4.000 und eine Glasübergangstemperatur (Tg) von -50° C bis -60° C aufweist.
  7. Verfahren nach Anspruch 6, worin die Polycarbonatdiolkomponente (B2) durch Umesterung von Diallylcarbonat mit 1,5-Pentandiol oder 1,6-Hexandiol oder mit einem Gemisch beider hergestellt wird.
  8. Verfahren nach Anspruch 6, worin die Polycarbonat-Copolyesterdiolkomponente (B2) durch Umesterung von Diallylcarbonat und Caprolacton mit 1,5-Pentandiol oder 1,6-Hexandiol oder einem Gemisch beider hergestellt wird.
  9. Verfahren nach Anspruch 6, worin die Polycarbonat-Copolyesterdiolkomponente (B2) durch Umesterung von Diallylcarbonat mit 1,5-Pentandiol oder 1,6-Hexandiol oder einem Gemisch beider und einem aliphatischen Polyesterdiol-Oligomer mit einem zahlenmittleren Molekulargewicht (Mn) von 350 bis 750 hergestellt wird, welches Oligomer durch Kondensieren einer aliphatischen Dicarbonsäure, ausgewählt unter Bernsteinsäure, Adipinsäure, Sebacinsäure und Dodecansäure, mit Neopentylglykol und 1,5-Pentandiol oder 1,6-Hexandiol oder einem Gemisch beider hergestellt wird.
  10. Verfahren nach Anspruch 1, worin die Diolkomponente (B3) ein zahlenmittleres Molekulargewicht (Mn) von 700 bis 3.000 aufweist.
  11. Verfahren nach Anspruch 10, worin die Polycarbonatdiolkomponente (B3) durch Umesterung von Diallylcarbonat mit Cyklohexandimethanol oder Tricyklohexandimethanol, gegebenenfalls in Anwesenheit eines aliphatischen Diols, hergestellt wird.
  12. Verfahren nach Anspruch 10, worin die Polycarbonat-Copolyesterdiolkomponente (B3) durch Umesterung von Diallylcarbonat mit Cyklohexandimethanol oder Tricyklohexandimethanol, gegebenenfalls in Anwesenheit eines aliphatischen Diols, und mit einem aromatischen Polyesterdiol-Oligomer mit einem zahlenmittleren Molekulargewicht (Mn) von 500 bis 1.000 hergestellt wird, welches Oligomer durch Kondensieren einer unter Phthalsäure, Isophthalsäure und Terephthalsäure ausgewählten Säure mit Cyklohexandimethanol oder Tricyklohexandimethanol hergestellt wird.
  13. Verfahren nach Anspruch 1, worin die Umsetzung der Diisocyanatkomponente (A) mit der Diolgemischkomponente (B) in Masse bei einer Temperatur von 60° C bis 100° C während einer Zeit von 0,5 bis 6 Stunden, gegebenenfalls in Anwesenheit eines Katalysators, ausgewählt unter den metallorganischen Verbindungen eines unter Zinn, Blei, Quecksilber und Titan ausgewählten Metalles, ausgeführt wird.
  14. Verfahren nach Anspruch 1, worin diese Zusammensetzung zusätzlich wenigstens ein Additiv enthält, ausgewählt unter Vernetzungskatalysatoren, Adhäsionspromotoren, anorganischen Füllstoffen, Antioxidentien, Stabilisatoren, Flammverzögerern und Klebrigmachern.
EP89202777A 1988-11-18 1989-11-06 Reaktive Schmelzzusammensetzung Expired - Lifetime EP0369517B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89202777T ATE92508T1 (de) 1988-11-18 1989-11-06 Reaktive schmelzzusammensetzung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT8822653A IT1227361B (it) 1988-11-18 1988-11-18 Composizione di hot melt reattivo.
IT2265388 1988-11-18

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EP0369517A1 EP0369517A1 (de) 1990-05-23
EP0369517B1 true EP0369517B1 (de) 1993-08-04

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US (1) US4996283A (de)
EP (1) EP0369517B1 (de)
JP (1) JP2802657B2 (de)
AT (1) ATE92508T1 (de)
CA (1) CA2003267A1 (de)
DE (1) DE68908091T2 (de)
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IT (1) IT1227361B (de)

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JP3150970B2 (ja) * 1991-01-25 2001-03-26 ミネソタ マイニング アンド マニュファクチャリング カンパニー 良好な接着性を有するイソシアネート末端ポリウレタン初期重合体の配合物
US5418288A (en) * 1991-07-18 1995-05-23 Mitsui Toatsu Chemicals, Inc. Isocyanate resin compositions and hot melt and pressure sensitive adhesives based thereon
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US7575653B2 (en) * 1993-04-15 2009-08-18 3M Innovative Properties Company Melt-flowable materials and method of sealing surfaces
EP0813979B1 (de) 1996-06-19 2001-09-19 H.B. Fuller Licensing & Financing, Inc. Thermoplastische Polyurethane für Buchbinderei
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US6767959B2 (en) * 2001-01-03 2004-07-27 Sika Ag, Vorm. Kaspar Winkler & Co. Adhesives with good mechanical properties, suitable for use with antennas
JP2003213237A (ja) * 2002-01-22 2003-07-30 Three M Innovative Properties Co 接着剤組成物
CN101163728B (zh) * 2005-04-22 2010-11-24 旭硝子株式会社 异氰酸酯基封端的氨基甲酸酯预聚物、其制备方法和包括该氨基甲酸酯预聚物的粘合剂
JP5013159B2 (ja) * 2005-12-06 2012-08-29 日本ポリウレタン工業株式会社 ポリウレタン樹脂の製造方法
WO2009072431A1 (ja) * 2007-12-03 2009-06-11 Mitsui Chemicals Polyurethanes, Inc. ラミネート用接着剤
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JP5761460B2 (ja) * 2012-12-20 2015-08-12 Dic株式会社 水蒸気バリア性接着剤用樹脂組成物、及び積層体
KR101752123B1 (ko) 2014-06-24 2017-06-28 미쓰비시 가가꾸 가부시키가이샤 폴리카보네이트디올의 제조 방법 및 폴리카보네이트디올 그리고 그것을 사용한 폴리우레탄
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WO2021045196A1 (ja) * 2019-09-04 2021-03-11 旭化成株式会社 硬化性組成物及び合成皮革
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JPH02199185A (ja) 1990-08-07
EP0369517A1 (de) 1990-05-23
IT8822653A0 (it) 1988-11-18
DE68908091T2 (de) 1993-12-09
CA2003267A1 (en) 1990-05-18
JP2802657B2 (ja) 1998-09-24
US4996283A (en) 1991-02-26
ATE92508T1 (de) 1993-08-15
IT1227361B (it) 1991-04-08
ES2044069T3 (es) 1994-01-01
DE68908091D1 (de) 1993-09-09

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